Polyoxymethylene fibers in concrete

ABSTRACT

Disclosed are polymeric additives for concrete formed of a polyoxymethylene (POM) copolymer. POM copolymers can be utilized to form fibrous additives for concrete, i.e., microfibers and/or macrofibers. The POM copolymers can include one or more chemical groups, e.g., end groups and/or pendant groups that can increase the polarity of the POM and increase the hydrophilicity of the formed fibers, which can improve miscibility of the fibers in wet concrete. Chemical groups of the POM copolymers can bond with components of the concrete or can hydrolyze to form groups that can bond with components of the concrete, e.g., form covalent or noncovalent (e.g., electrostatic or ionic) bonds with one or more components of the concrete binder.

CROSS REFERENCE TO RELATED APPLICATION

This application claims filing benefit of U.S. Provisional PatentApplication Ser. No. 61/423,659 having a filing date of Dec. 16, 2010,which is incorporated herein by reference in its entirety.

BACKGROUND

Concrete is the most commonly used man-made construction material in theworld. Concrete includes a binder component and an aggregate component.The binder component is cement, which is generally formed of a calcinedlimestone-based composite, and the aggregate component is generallyformed of quartz sand or calcium carbonate.

Improvements in the properties of concrete have been obtained in thepast by combining the concrete with modifying additives. Commonmodifications to improve concrete include the addition of fibrousmaterials to the binder such as metal, polymeric, glass, and naturalfibers, and formation in conjunction with rebar. Synthetic fibers havebeen used for several decades as a reinforcing agent for concrete,particularly for slab on grade applications. Fiber reinforced concretecan exhibit decreased shrinkage, decreased permeability and evenincreased abrasion and shatter resistance, depending upon the specificmaterials used in the composite.

The nature of the fiber reinforcement can vary. Microfibers, rangingfrom about 1 to about 10 denier are typically used to help preventplastic shrinkage cracking as the concrete sets. The presence of themicrofibers at loadings of about 1 to 3 pounds per cubic yard (lb/yd³)of concrete prevents micro-cracking of the concrete in the first 24 to48 hours after pouring, as the bulk of the water in the mixtureevaporates. Fibrillated or embossed macrofibers in the range of about1000 denier are often added at loadings of 3 to 8 lb/yd³ as a secondaryreinforcement. These fibers are added to improve overall toughness, asquantified by measurements of residual strength after first break onconcrete samples containing the fibers (e.g., as measured according toASTM C-1399). In both cases, the fibers ideally can be easily mixed withthe wet concrete mixture and resist separating during the finishing andsetting steps. Level of property enhancements to the concrete depends onboth the strength of the fiber and adhesion between the fiber and theconcrete matrix.

Polypropylene has been the material of choice by the concrete industryfor both micro- and macrofibers. Polypropylene fibers can be easilyformed via melt spinning (both micro- and macrofibers) or cutting fromthin films (e.g., tape fibers or fibrillated fibers). Polypropylenefibers can exhibit tenacity on the order of 5 grams-force per denier(g/den). In addition, polypropylene is alkali resistant, which iscritically important for any concrete additive (pH of concrete istypically 11 or higher). However, polypropylene does have disadvantages.Its low density and hydrophobicity combine to make it tend to bloom tothe surface during finishing. This can cause surface appearanceproblems. Further, polypropylene fibers will not chemically bond toconcrete, and rely only on mechanical interactions for adhesion to thematrix.

Other materials have been tried in an attempt to mitigate thedisadvantages of polypropylene fiber additives. Polyamide fibers havebeen examined as polyamide is a denser material and thus expected toresist surface bloom. However, the moisture absorption of polyamides,resulting in lower strength and modulus, rendered these fibers lesseffective overall in concrete applications. Polyvinyl alcohol (PVA)fibers have also been developed for use in concrete. The obviousadvantage is the potential for chemical bonding between the concretematrix and pendant —OH groups on the polymer backbone. However, thissought-after bonding actually led to additional problems. In fact,pretreatment of PVA fibers with formaldehyde (HCHO_((aq))) to bind afraction of the —OH groups as the cyclic formal was found to benecessary to reduce the fiber—concrete interaction and reduce stress inthe cured concrete product. In addition, PVA fibers are quite expensiveand successful utilization requires an on-site, multistep mixing processwith the concrete. Despite these difficulties, PVA fibers have foundlimited use in specialty concrete applications, such as precast concretefor earthquake-proof structures. Its use beyond these specialtyapplications has been quite limited.

While there have been improvements in composite materials incorporatingfibrous polymeric materials, there remains room for further improvementand variation within the art. Fibrous polymeric modifiers and methods ofusing the modifiers with concrete that can provide further structuralimprovements to construction materials would be beneficial.

SUMMARY

According to one embodiment, disclosed is a concrete that includes anaggregate, a cementitious binder, and a plurality of discrete fibers.The fibers include a polyoxymethylene (POM) copolymer in an amount of atleast about 50% by weight of the fibers and exhibit a water contactangle of less than about 30°, or less than about 20° in one embodiment.

The copolymer can include a high number of hydroxyl terminal groups. Forinstance, at least about 50% of the terminal groups of the POM copolymercan be hydroxyl groups. In one embodiment, an individual copolymer chaincan include between about 15 and about 20 terminal hydroxyl groups.

The POM copolymer can be the product of a copolymerization reaction oftrioxane with a monomer. Representative monomers include a cyclic acetalcontaining at least one O(CH₂)_(n) group where n is greater than 1, acyclic formal having pendant acrylate or substituted acrylate estergroups, a cyclic ester, glycerol formal acetate, and glycerol formalformate.

The fibers can be microfibers and/or macrofibers. For instance, theconcrete can include microfibers in an amount up to about 3 pounds percubic yard and can include macrofibers in an amount up to about 8 poundsper cubic yard.

Also disclosed is a method of forming concrete. A method can includedispersing a plurality of discrete fibers as described herein throughoutthe concrete. The fibers can be premixed with a component of theconcrete. For instance, the fibers can be mixed with dry cement or withwet cement prior to further mixing with the aggregate.

BRIEF DESCRIPTION OF THE FIGURES

A full and enabling disclosure of the present disclosure, including thebest mode thereof, to one of ordinary skill in the art, is set forthmore particularly in the remainder of the specification, includingreference to the accompanying figures in which:

FIG. 1 schematically illustrates one method for forming a fiber asdescribed herein.

FIG. 2 compares water contact angle for three different microfibers, oneof the microfibers was formed of polypropylene and the other two wereformed of polyoxymethylene (POM) copolymers.

FIG. 3 compares the change in compressive strength with fiber loadinglevel for concrete samples including different microfibers, one concretesample included microfibers formed of polypropylene and the other twoconcrete samples included microfibers formed of POM copolymers.

DETAILED DESCRIPTION

It is to be understood by one of ordinary skill in the art that thepresent discussion is a description of exemplary embodiments only, andis not intended as limiting the broader aspects of the presentdisclosure.

In general, disclosed herein are polymeric additives for concrete formedof a polyoxymethylene (POM) copolymer. More specifically, POM copolymerscan be utilized to form fibrous additives for concrete, i.e.,microfibers and/or macrofibers. The POM fibers can mix well with wetconcrete and resist surface blooming during concrete set. In oneembodiment, POM copolymers utilized to form the fibrous additives caninclude one or more chemical groups, e.g., end groups and/or pendantgroups that can further improve integration of the fibrous additivesformed of the polymer with the wet concrete. Chemical groups encompassedherein include groups that can increase the polarity of the POM andincrease the hydrophilicity of the formed fibers, which can improvemiscibility of the fibers in wet concrete. Also encompassed herein arechemical groups that can bond with components of the concrete or canhydrolyze to form groups that can bond with components of the concrete,e.g., form covalent or noncovalent (e.g., electrostatic or ionic) bondswith one or more components of the concrete binder, so as to furtherimprove strength characteristics of the concrete.

In general, POM polymers for use in forming disclosed additives can becopolymers that can exhibit resistance to the alkali nature of concrete.As used herein and in the accompanying claims, the term “copolymer” isintended to encompass any polymer having, as at least part of thepolymer chain, structural units derived from trioxane and cyclic formalsor their functionalized derivatives. Thus, the term “copolymer” as usedherein and in the accompanying claims is intended to encompassterpolymers, tetrapolymers, and the like that include structural unitsin the polymer chain derived from trioxane and cyclic formals or theirfunctionalized derivatives in addition to other units, if present duringpolymerization. For instance, other units can be derived from trioxaneor a mixture of trioxane and dioxolane and cyclic formals, e.g., cyclicether and cyclic acetal monomers.

A copolymerization process can include synthesis of the POM-formingmonomers. For instance, trioxane can first be formed by thetrimerization of formaldehyde in an aqueous phase, and subsequentseparation and purification of the formed monomer.

In one embodiment, a POM copolymer can be manufactured by thecopolymerization of trioxane with 0.2 to 6 parts per 100 parts oftrioxane of cyclic acetal containing at least one O(CH₂)_(n) group wheren>1. In general, the POM copolymer can include at least 50 mol-%, suchas at least 75 mol-%, such as at least 90 mol-% and such as even atleast 95 mol-% of —CH₂O-repeat units.

The copolymerization can be initiated by cationic initiator as isgenerally known in the art, such as organic or inorganic acids, acidhalides, and Lewis acids. One example of the latter is boron fluorideand its coordination complexes with organic compounds in which oxygen orsulfur is the donor atom. The coordination complexes of borontrifluoride may, for example, be a complex with a phenol, an ether, anester, or a dialkyl sulfide. Boron trifluoride etherate (BF₃.Et₂O) isone preferred coordination complex useful in the cationiccopolymerization processes. Alternately, gaseous BF₃ may be employed asthe polymerization initiator.

Catalyst concentration may be varied within wide limits, depending onthe nature of the catalyst and the intended molecular weight of thecopolymer. For example, catalyst concentration may range from about0.0001 to about 1 weight percent, and in one embodiment can range fromabout 0.001 to about 0.1 weight percent, based on the total weight ofthe monomer mixture.

A chain transfer agent can also be utilized during polymerization of themonomers. In general, a relatively small amount of a chain transferagent can be used, e.g., about 100 to about 1000 ppm.

In one embodiment, the chain transfer agent can be an acetal such asmethylal, butylal, mixtures of acetals, and the like. Other typicalchain transfer agents such as esters or alcohols including methylformate, methanol, and so forth may be used. Utilization of such chaintransfer agents can form a POM copolymer that can be used to form afibrous additive for concrete that can show multiple improvements ascompared to previously known fibrous additives. For instance, the POMcopolymer can exhibit increased density as compared to polymers such aspolypropylene that have been used to form fibrous additives in the past.Fibers formed from a higher density polymer can be less likely to bloomto the surface of the wet concrete during set. Accordingly, the fiberscan remain distributed throughout the concrete following cure to provideimproved strength characteristics to the concrete.

In addition, fibers formed of the POM copolymers can exhibit increasedhydrophilicity as compared to fibers formed of more traditionalpolymers, such as polypropylene. For instance, and as discussed below inthe examples section, a trioxane/cyclic acetal POM copolymer formed witha methylal chain transfer agent can have a water contact angle of lessthan about 30°, or less than about 25° in one embodiment. As comparison,polypropylene generally has a water contact angle of greater than 35°.The increased hydrophilicity of the POM copolymer can improve mixingbetween POM polymeric fibers and the wet concrete and can also preventblooming of the fibers to the surface of the concrete during cure.

A POM copolymer can be formed so as to further enhance the beneficialaspects of the material. For instance, a POM copolymer can be formed toinclude terminal groups, which can include both end group and side orpendant functional groups, such as hydroxyl groups, so as to furtherimprove the hydrophilicity of the polymer. In one embodiment, terminalgroups can provide binding sites for formation of bonds between thefibrous additives and components of the concrete matrix. For instance,terminal hydroxyl groups can provide electrostatic binding withcomponents of the concrete binder.

According to one embodiment, a POM copolymer can be formed to include arelatively high number of terminal hydroxyl groups on the copolymer. Forexample, the POM copolymer can have terminal hydroxyl groups, forexample hydroxyethylene groups and/or hydroxyl groups, in greater thanabout 50% of all the terminal sites on the polymer, which includes bothpolymer end groups and terminal side, or pendant, groups. For instance,greater than about 70%, greater than about 80%, or greater than about85% of the terminal groups on the POM copolymer may be hydroxyl groups,based on the total number of terminal groups present. In one embodiment,up to about 90%, or up to about 85% of the terminal groups on the POMcopolymer may be hydroxyl groups. In one preferred embodiment, a POMcopolymer can include up to about 20 hydroxyl groups per polymer chain,for instance, between about 15 and about 20 hydroxyl groups per chain.

The POM copolymer can have a content of terminal hydroxyl groups of atleast about 5 mmol/kg, such as at least about 10 mmol/kg, such as atleast about 15 mmol/kg. For example, the terminal hydroxyl group contentranges from about 18 to about 50 mmol/kg.

Through formation of additional terminal hydroxyl groups, the copolymercan exhibit increased hydrophilicity. For example, fibers including aPOM copolymer that includes a relatively high percentage of terminalhydroxyl groups can exhibit a water contact angle of Less than about25°, less than about 20°, or less than about 15°. For instance, thefibers can exhibit a contact angle of less than about 21°, in oneembodiment.

A POM copolymer can be formed to include a high percentage of terminalhydroxyl groups through selection of the chain transfer agent usedduring polymerization. For instance, a glycol chain transfer agent suchas ethylene glycol, diethylene glycol, mixtures of glycols, and the likecan be used in a copolymerization of trioxane with a cyclic acetalcontaining at least one O(CH₂)_(n) group where n>1. According to thisembodiment, greater than about 80%, for instance greater than about 85%of the terminal end groups on the formed POM copolymer can beethoxyhydroxy or —OCH₂CH₂OH (—C₂OH) end groups. This type of POMcopolymer (i.e., trioxane copolymerized with a cyclic acetal in thepresence of an ethylene glycol chain transfer agent) is referred tothroughout this disclosure as POM-OH.

A POM copolymer can be formed from polymerization of one or moremonomers that can produce on the copolymer terminal groups that canprovide desirable characteristics to the fibrous concrete additivesformed of the POM copolymers. For example, a copolymer can be formed soas to include terminal and/or pendant groups including, withoutlimitation, alkoxy groups, formate groups, acetate groups and/oraldehyde groups. The terminal groups can be functional as formed, e.g.,the terminal groups of the as-formed polymer can increase hydrophilicityof the POM copolymer and/or can provide bonding sites for bonding withone or more components of the concrete. Alternatively, the formedcopolymer can be further treated to form terminal groups useful in theformed concrete additives. For example, following formation, thecopolymer can be subjected to hydrolysis to form the desired terminalgroups on the copolymer.

Without wishing to be bound to any particular theory, it is believedthat the formation of additional reactive terminal groups (i.e., endgroups and pendant groups) on a POM polymer can encourage bond formationbetween the POM copolymer and components of the cement binder. Forinstance, Portland cement is a complex mixture of di- and tricalciumsilicates, tricalcium aluminate, and a smaller amount of a ferritephase. Accordingly, the hydroxyl groups of a polymer can bond —Si—OH,Al—OH, and Fe—OH moieties of a Portland cement. Similar binding can takeplace with other binders as are known in the art.

Any of a variety of different monomers can be copolymerized with one ormore other POM-forming monomers, e.g., trioxane. Monomers can include,without limitation, cyclic formals having pendant acrylate orsubstituted acrylate ester groups, cyclic ethers, cyclic acetals, and soforth. By way of example, trioxane can be copolymerized with1,2,6-hexanetriol formal or its ester derivatives, as described in U.S.Pat. No. 4,975,518 to Broussard, et al.; ester derivatives glycerolformal, as described in U.S. Pat. No. 4,975,519 to Yang, et al.;glycidyl ester derivatives, as described in U.S. Pat. No. 4,983,708 toYang, et al.; and trimethylolpropane formal derivatives, as described inU.S. Pat. No. 5,004,798 to Broussard, et al. (all patents areincorporated herein by reference). Monomers can include, withoutlimitation, α,α- and α,β-isomers of glycerol formal, such as glycerolformal acetate (GFA), glycerol formal methacrylate, glycerol formalcrotonate, and glycerol formal chloroacetate; glycerol formal formate(GFF); 1,2,6-hexanetriol formal acetate; glycidyl acrylate;5-ethyl-5-hydroxymethyl-1,3-dioxane (EHMDO); EHMDO ester of acetic acid;EHMDO ester of acrylic acid; EHMDO ester of 3-choro-propanoic acid;EHMDO ester of 2-methylacrylic acid; EHMDO ester of 3-methylacrylicacid; EHMDO ester of undedocenoic acid; EHMDO ester of cinnamic acid;EHMDO ester of 3,3-dimethylacrylic acid; and so forth.

A monomer can include a terminal group that is much less reactive duringpolymerization as compared to the formal group itself or the trioxane,e.g., an ester group, a formate group, or an acetate group. Accordingly,the terminal group can remain unreacted during polymerization to form anessentially linear polymer with side chain functionality. This sidechain functionality can be suitable for use as is or, alternatively, canbe hydrolyzed following polymerization to yield pendant hydroxylfunctional groups. Hydrolysis following polymerization can also removeunstable hemiacetal end groups and improve the stability of theresulting copolymers.

In one preferred embodiment, a POM copolymer can be formed via thecopolymerization of trioxane with between about 0.2 and about 6 partsGFF per 100 parts trioxane or 0.2 to 6 parts of a combination of1,3-dioxolane and GFF per 100 parts trioxane, using ethylene glycol asthe chain transfer agent. This copolymer, following hydrolysis, can haveabout 80% or higher —C₂OH end groups and up to 20 to 30 pendant —OHgroups per chain. This copolymer is referred to throughout thisdisclosure as lateral-OH POM.

Multiple monomers may be employed in forming the disclosed copolymers soas to form tri- or tetra-polymers. For instance, a trioxane can bepolymerized with a mixture of dioxolane and one or more of the cyclicformals described above. Additional monomers as are generally known inthe art can be incorporated in disclosed copolymer. Exemplary monomerscan include ethylene oxide, 1,3-dioxolane, 1,3-dioxepane,1,3-dioxep-5-ene, 1,3,5-trioxepane, and the like.

The polymerization can be carried out as precipitation polymerization orin the melt. By a suitable choice of the polymerization parameters, suchas duration of polymerization or amount of chain transfer agent, themolecular weight and hence the melt index value of the resulting polymercan be adjusted. The target melt index of a POM copolymer can be betweenabout 2 decigrams per minute (dg/min) and about 30 dg/min, between about5 dg/min and about 20 dg/min, or between about 8 dg/min and about 10dg/min.

Following formation, a polymeric composition including the POM copolymercan be processed to form a fibrous additive for concrete. A polymericcomposition can include components in addition to the POM copolymer. Theamount of the POM copolymer present in a polymeric composition can vary.In one embodiment, for instance, the composition contains the POMcopolymer in an amount of at least about 50% by weight, such as in anamount greater than about 60% by weight, such as in an amount greaterthan about 65% by weight, such as in an amount greater than about 70% byweight. In general, the POM copolymer is present in an amount less thanabout 95% by weight, such as in an amount less than about 90% by weight,such as in an amount less than about 85% by weight.

Additives as may be incorporated in a polymeric composition can includeother polyoxymethylene homopolymers and/or polyoxymethylene copolymers.Such polymers, for instance, are generally unbranched linear polymerswhich contain as a rule at least 80%, such as at least 90%, oxymethyleneunits.

In addition to the POM copolymer, the polymeric composition can includean impact modifier and a coupling agent if desired for an attachmentbetween a POM polymer and the impact modifier. The impact modifier maycomprise a thermoplastic elastomer. In general, any suitablethermoplastic elastomer may be used. In one embodiment, for instance,the thermoplastic elastomer may include reactive groups that directly orindirectly attach to reactive groups contained on a POM polymer (i.e.,either the POM copolymer as described above or additional POM polymersincorporated in the polymeric composition). For instance, thethermoplastic elastomer can have active hydrogen atoms which allow forcovalent bonds to form with the hydroxyl groups on the polyoxymethyleneusing a coupling agent.

Thermoplastic elastomers well suited are polyester elastomers (TPE-E),thermoplastic polyamide elastomers (TPE-A) and thermoplasticpolyurethane elastomers (TPE-U). The above thermoplastic elastomers haveactive hydrogen atoms which can be reacted with the coupling reagentsand/or the polyoxymethylene polymer. Examples of such groups areurethane groups, amido groups, amino groups or hydroxyl groups. Forinstance, terminal polyester diol flexible segments of thermoplasticpolyurethane elastomers have hydrogen atoms which can react, forexample, with isocyanate groups.

The amount of impact modifier contained in a polymeric composition canvary depending on many factors. In general, one or more impact modifiersmay be present in the composition in an amount greater than about 5% byweight, such as in an amount greater than about 10% by weight. Theimpact modifier is generally present in an amount less than 30% byweight, such as in an amount less than about 25% by weight, such as inan amount up to about 18% by weight in order to provide sufficientimpact strength resistance to the material.

When present, a coupling agent in the polymeric composition comprises acoupling agent capable of coupling the impact modifier to a POM polymer.A wide range of polyfunctional, such as trifunctional or bifunctionalcoupling agents, may be used. The coupling agent may be capable offorming covalent bonds with the terminal hydroxyl groups on a POMpolymer and with active hydrogen atoms on the impact modifier. In thismanner, the impact modifier becomes coupled to the POM through covalentbonds.

In one embodiment, the coupling agent comprises a diisocyanate, such asan aliphatic, cycloaliphatic and/or aromatic diisocyanate. The couplingagent may be in the form of an oligomer, such as a trimer or a dimer. Inone embodiment, an aromatic polyisocyanate is used, such as4,4′-diphenylmethane diisocyanate (MDI).

When present, a polymer composition can include a coupling agent in anamount from about 0.1% to about 10% by weight. In one embodiment, forinstance, the coupling agent is present in an amount greater than about1% by weight, such as in an amount greater than 2% by weight. In oneparticular embodiment, the coupling agent is present in an amount fromabout 0.2% to about 5% by weight.

A formaldehyde scavenger may also be included in a polymericcomposition. The formaldehyde scavenger, for instance, may beamine-based and may be present in an amount less than about 1% byweight.

A polymeric composition can optionally contain a stabilizer and/orvarious other known additives. Such additives can include, for example,viscosity reducing agents, antioxidants, acid scavengers, UV stabilizersor heat stabilizers, adhesion promoters, lubricants, nucleating agents,demolding agents, fillers, reinforcing materials or antistatic agentsand additives which impart a desired property to the material, such asdyes and/or pigments.

In general, other additives can be present in the polymeric compositionin an amount up to about 10% by weight, such as from about 0.1% to about5% by weight, such as from about 0.1 to about 2% by weight.

The components of the polymeric composition can be melt blendedtogether. In one embodiment, melt blending of the components can causereaction to occur between individual components, such as a couplingagent, a POM polymer, and an impact modifier. Reaction betweencomponents can occur simultaneously or in sequential steps.

In one embodiment, the different components can be melted and mixedtogether in a conventional single or twin screw extruder. The meltblending of the components is typically carried out at temperatures offrom about 100° C. to about 240° C., such as from about 150° C. to about220° C., and the duration of mixing is typically from about 0.5 to about60 minutes.

Following formation, the polymeric composition can be used as formed toprepare a fibrous additive for concrete or may be formed for laterprocessing. For instance, extruded strands may be produced by anextruder which are then pelletized and stored for later use. Prior tocompounding, the polymer components may be dried to a moisture contentof about 0.05 weight percent or less. If desired, the pelletizedcompound can be ground to any suitable particle size, such as in therange of from about 100 microns to about 500 microns.

Manufacturing processes for forming fibers from the POM generally neednot vary with the specific POM copolymers utilized in forming thecomposition, e.g., POM, POM-OH or lateral-OH POM.

For purposes of this disclosure, a monofilament fiber is herein definedto refer to a fiber that has been extruded or spun from a melt as anindividual fiber. That is, while the extruded monofilament fiber can besubjected to post-extrusion processing (e.g., quenching, drying,drawing, heat processing, finish application, etc.), the fiber will beinitially extruded or spun from a melt in the individual fiber form. Atape fiber, on the other hand, is intended to refer to fibers that havebeen formed from a larger section during post-extrusion processing. Forexample, the term ‘tape fiber’ can encompass fibers that have been cutor otherwise separated from a larger extruded film, for instance anextruded flat film or a film extruded as a cylinder. In general, tapefibers can have a clear delineation between adjacent sides of thefibers, with a clear angle between the adjacent sides, as they canusually be formed by cutting or slicing individual fibers from thelarger polymer section, but this is not a requirement. For example, inone embodiment, individual tape fibers can be pulled from a largerpolymeric piece, and thus may not show the sharper angles betweenadjacent edges that may be common to a tape fiber that has been cut froma larger piece of material.

Referring to FIG. 1, one embodiment of a POM fiber forming processgenerally 10 is schematically illustrated. According to the illustratedembodiment, a melt of a POM composition can be provided to an extruderapparatus 12.

The extruder apparatus 12 can be a melt spinning apparatus as isgenerally known in the art. For example, the extruder apparatus 12 caninclude a mixing manifold 11 in which a POM composition can be mixed andheated to form a molten composition. The formation of the molten mixturecan generally be carried out at a temperature as described above, e.g.,from about 100° C. to about 240° C.

Optionally, to help ensure the fluid state of the molten mixture, in oneembodiment, the molten mixture can be filtered prior to extrusion. Forexample, the molten mixture can be filtered to remove any fine particlesfrom the mixture with a filter of between about 180 and about 360 gauge.

Following formation of the molten mixture, the mixture can be conveyedunder pressure to the spinneret 14 of the extruder apparatus 12, whereit can be extruded through an orifice to form the fiber 9. The mixturecan be extruded as either a monofilament fiber 9, as shown in FIG. 1, oras a film, for instance in either a sheet orientation or in acylindrical orientation, and cut or sliced into individual tape fibersduring post-processing of the film. In particular, while the majority ofthe ensuing discussion is specifically directed to the formation of amonofilament fiber, it should be understood that the below describedprocesses are also intended to encompass the formation of a film forsubsequent formation of a tape fiber.

The spinneret 14 can generally be heated to a temperature that can allowfor the extrusion of the molten polymer while preventing breakage of thefiber 9 during formation. For example, in one embodiment, the spinneret14 can be heated to a temperature of between about 125° C. and about210° C. In one embodiment, the spinneret 14 can be heated to the sametemperature as the mixing manifold 11. This is not a requirement of theprocess, however, and in other embodiments, the spinneret 14 can be at adifferent temperature than the mixing manifold 11. For example, in oneembodiment, increasing temperatures can be encountered by the mixture asit progresses from the inlet to the mixing manifold to the spinneret. Inone embodiment, the mixture can progress through several zones prior toextrusion.

When forming a monofilament fiber, the spinneret orifice through whichthe polymer can be extruded can generally be less than about 2.5 mm inmaximum cross-sectional width (e.g., diameter in the particular case ofa circular orifice). For example, in one embodiment, when forming amacrofiber, the spinneret orifices can be between about 1 mm and about2.5 mm in maximum cross-sectional width. When forming a microfiber, thespinneret orifices can be between about 0.6 mm and about 1.5 mm inmaximum cross-sectional width.

When forming a film, the film die can be of any suitable orientation andlength, and can be set to a thickness of less than about 2.5 mm. Forexample, in one embodiment, the film die can be set at a width ofbetween about 1 mm and about 2.5 mm.

Following extrusion of the polymer, the un-drawn fiber 9 can bequenched, for instance in a liquid bath 16 and directed by roll 18. Theliquid bath 16 in which the fiber 9 can be quenched can be a liquid inwhich the polymer is insoluble. For example, the liquid can be water,ethylene glycol, or any other suitable liquid as is generally known inthe art. Generally, in order to encourage formation of fibers withsubstantially constant cross-sectional dimensions along the fiberlength, excessive agitation of the bath 16 can be avoided during theprocess. Of course, a liquid quench is not a requirement of disclosedprocesses, and in another embodiment, the un-drawn fiber can be quenchedin an air quench, as is known.

Roll 18 and roll 20 can be within bath 16 and convey fiber 9 through thebath 16. Dwell time of the material in the bath 16 can vary, dependingupon particular materials included in the polymeric material, particularline speed, etc. In general, fiber 9 can be conveyed through bath 16with a dwell time long enough so as to ensure complete quench, i.e.,crystallization, of the polymeric material. For example, in oneembodiment, the dwell time of the material in the bath 16 can be betweenabout 30 seconds and about 2 minutes.

At or near the location where the fiber 9 exits the bath 16, excessliquid can be removed from the fiber 9. This step can generally beaccomplished according to any process known in the art. For example, inthe embodiment illustrated in FIG. 1, the fiber 9 can pass through aseries of nip rolls 23, 24, 25, 26 to remove excess liquid from thefiber. Other methods can be alternatively utilized, however. Forexample, in other embodiments, excess liquid can be removed from thefiber 9 through utilization of a vacuum, a press process utilizing asqueegee, one or more air knives, and the like.

According to another embodiment, the extruded fiber can be quenchedaccording to an air cooling procedure. According to this embodiment, anextruded fibers can be carried out under an air flow at a pre-determinedtemperature, for instance between about 30° C. and about 80° C., orabout 50° C. in one embodiment.

In one embodiment, a lubricant can be applied to the fiber 9. Forexample, a spin finish can be applied at a spin finish applicator chest22, as is generally known in the art. In general, a lubricant can beapplied to the fiber 9 at a low water content. For example, a lubricantcan be applied to the fiber 9 when the fiber is at a water content ofless than about 75% by weight. Any suitable lubricant can be applied tothe fiber 9. For example, a suitable oil-based finish can be applied tothe fiber 9, such as Lurol PP-912, available from GhoulstonTechnologies, Inc. Addition of a finishing or lubricant coat on thefiber can, in some embodiments, improve handling of the fiber duringsubsequent processing and can also reduce friction and staticelectricity build-up on the fiber.

After quenching of the fiber 9 and any optional process steps, such asaddition of a lubricant for example, the fiber can be drawn whileapplying heat. For example, in the embodiment illustrated in FIG. 1, thefiber 9 can be drawn in an oven 43 heated to a temperature of betweenabout 100° C. and about 175° C. Additionally, in this embodiment, thedraw rolls 32, 34 can be either interior or exterior to the oven 43, asis generally known in the art. In another embodiment, rather thanutilizing an oven as the heat source, the draw rolls 32, 34 can beheated so as to draw the fiber while it is heated. For example, the drawrolls can be heated to a temperature of between about 150° C. and about190° C. In another embodiment, the fiber can be drawn over a hotplateheated to a similar temperature or by passing through a heated liquidbath.

The fiber can be drawn in a first (or only) draw at a high draw ratio.For example, the fiber 9 can be drawn with a draw ratio (defined as theratio of the speed of the second or final draw roll 34 to the first drawroll 32) of greater than about 5. For instance, in one embodiment, thedraw ratio of the first (or only) draw can be greater than about 8. Inanother embodiment, the draw ratio can be up to about 10. Additionally,the fiber can be wrapped on the rolls 32, 34 as is generally known inthe art. For example, in one embodiment, between about 5 and about 15wraps of the fiber can be wrapped on the draw rolls.

A multi-stage draw can optionally be utilized. For instance, in a twostage draw, a fiber can be drawn to about 3 to about 15 times theoriginal length in a first stage at a temperature of between about 60°C. and about 160° C., or between about 120° C. and about 150° C. inanother embodiment. In a second stage draw, the fiber can be drawn fromabout 1.05 to about 6 times the length of the fiber following the firststage draw, or from about 1.05 to about 2 times the length of the fiberfollowing the first stage draw in another embodiment. The second drawcan generally be carried out at a temperature that is higher than thetemperature of the first stage draw, for example between about 100° C.and about 165° C., or from about 150° C. to about 160° C. in anotherembodiment.

Multi-stage drawing processes can be carried out in similar or differentenvironments. For instance, a first stage draw can be carried out in aheated oven, and a second stage can be carried out in a heated liquidbath. Multi-stage draws can include two, three, or higher numbers ofstages can be utilized. In one embodiment, a three stage draw can beused in which the fiber can be subjected to a first draw in air, asecond draw in a heated aqueous bath and a third draw in a heatedorganic solution (e.g., an oil).

While the embodiment of FIG. 1 utilizes a series of draw rolls forpurposes of drawing the fiber, it should be understood that any suitableprocess that can place a force on the fiber so as to elongate the fiberfollowing the quenching step can optionally be utilized. For example,any mechanical apparatus including nip rolls, godet rolls, steam cans,air, steam, or other gaseous jets can optionally be utilized to draw thefiber.

Following the drawing step, the drawn fiber 30 can be cooled and woundon a take-up roll 40. In other embodiments, however, additionalprocessing of the drawn fiber 30 may be carried out.

Optionally, the drawn fiber can be heat set. For example, the fiber canbe relaxed or subjected to a very low draw ratio (e.g., a draw ratio ofbetween about 0.7 and about 1.3) and subjected to a temperature ofbetween about 140° C. and about 170° C. for a short period of time,generally less than about 3 minutes. In some embodiment, a heat settingstep can be less than one minute, for example, about 0.5 seconds. Thisoptional heat set step can serve to “lock” in the crystalline structureof the fiber following drawing. In addition, it can reduce heatshrinkage.

The drawn fiber can be surface treated to improve certaincharacteristics of the fiber, such as wettability or adhesion, forexample. For instance, the fiber can be fibrillated, subjected to plasmaor corona treatments, or can include an added surface fiber sizing, allof which are generally known in the art, to improve physicalcharacteristics of the fiber.

In an embodiment in which a film is formed at the extruder, a tape fibercan be formed from the film either before or after the draw step, asdesired. For example, in one embodiment the film can be subjected to adrawing step, and the drawn film can be further processed to form thetape fibers of the present invention. In another embodiment, the filmcan be processed to form the tape fibers first, and then the formedfibers can be drawn, as described above for a monofilament fiber. Ineither case, the tape fibers can be cut or formed from the filmaccording to any process as is generally known in the art including, forexample, use of metal blades, rotary knives, and the like.

In general, the finished fiber 30 can be wound on a spool or take-upreel 40, as shown, and transported to a second location for formation ofthe fibrous additives. In an alternative embodiment, however, the fibercan be fed to a second processing line, where the fiber can be furtherprocessed to form the fibrous additives.

Following the drawing of the fiber, a drawn fiber including a POMcopolymer as described can exhibit a tenacity of greater than about 5g/den, for instance greater than about 10 g/den. In one embodiment, adrawn fiber can exhibit a tenacity of less than about 15 g/den, forinstance between about 5 g/den and about 15 g/den, or between about 5g/den and about 10 g/den, in another embodiment.

According to one embodiment, the fibers can be utilized as-formed asreinforcement material for concrete. In another embodiment, followingformation, a fiber can be further processed prior to use as areinforcement material in concrete. For Instance, fibers can be chopped,fibrillated, flattened, bent, or otherwise deformed prior to combinationwith concrete or a component thereof.

As used herein, the term ‘concrete’ generally refers to an artificialmaterial formed from one or more course aggregates mixed with water, acementitious binder, and any suitable modifiers. The aggregate maycomprise a quartz sand or calcium carbonate, or other suitableaggregate. The binder may include, for instance, Portland cement orgypsum. Traditional concrete generally has a density of between about2000 kilogram per cubic meter (kg/m³) and about 2500 kg/m³. Foamedconcrete is also encompassed by the term. Foamed concrete incorporates afoaming agent during the formation process and is much lighter thantraditional concrete, generally having a density of between about 400kg/m³ and about 1600 kg/m³. The term ‘concrete’ encompasses, withoutlimitation, hydratable cementitious compositions including ready-mix orpre-cast concrete, masonry concrete, shotcrete, bituminous concrete,gypsum compositions, cement-based fireproofing compositions, and thelike. The binder can be present in the cementitious composition in anamount greater than about 5% by weight of the concrete, or greater thanabout 20% by weight. In one embodiment, the binder can be present in anamount up to about 50%, or up to 80% by weight of the concrete. Whendescribing the cementitious composition, the above percentages by weightare based upon the weight percentage of dry material and thus excludeswater if present in the product.

Fibrous reinforcement materials can include fibers of any suitable sizeand geometry. By way of example, individual microfibers of between about1 denier and about 10 denier, for instance less than about 5 denier, orless than about 3 denier, can be included in concrete. Macrofibers, forexample fibers between about 500 denier and about 4000 denier, can beutilized as fibrous reinforcement as described herein. For instance,macrofibers of about 1000 denier, or greater than about 1000 denier orgreater than about 1200 denier. Macrofibers can be less than about 2500denier, or less than about 1800 denier. Fibers including a round crosssectional geometry can be preferred in some embodiments, but this is nota requirement, and micro- and/or macro-fibers of a noncircular crosssectional shape, and/or crimped fibers, as well as fibrous meshreinforcements can be preferred in other embodiments. Mixtures ofdifferent POM fibers can also be utilized, which can be combined withconcrete at the same time or sequentially, as desired.

In one embodiment, a concrete mixture can include a multitude ofrelatively short lengths of the fibers distributed throughout thematrix. For example, a concrete mixture can include monofilament fibersand/or tape fibers that have been cut or chopped to a length of lessthan about 5 inches. In one embodiment, the fibers can be less thanabout 3 inches in length, for instance, less than about 1 inch inlength.

POM fibrous additives can be added at relatively low loading levels andcan provide significant improvement to concrete. For instance, POMmacrofibers can be added at a level up to about 8 lb/yd³, or up to about5 lb/yd³ in one embodiment, or greater than about 2 lb/yd³, or greaterthan about 3 lb/yd³. POM microfibers can generally be added at lowerloading levels than POM macrofibers. For instance, POM microfibers canbe added at a level up to about 3 lb/yd³, or up to about 2 lb/yd³ in oneembodiment, or greater than about 1 lb/yd³, or greater than about 0.5lb/yd³

POM fibrous additives can be blended with wet cement while consideringseveral variables including temperature, time, concentration, type ofmaterial, and the like, according to known practices so as to obtain acomposite including the fibers randomly distributed throughout thecomposite with little or no agglomeration. Generally, a predeterminedamount of POM fibrous additives can be added to concrete during theregular mixing phase of the preparation. For instance, POM fibrousadditives can be added to concrete, or a component of the concrete,either in a dry-phase addition or a wet-phase addition.

In a dry-phase addition, POM fibrous additives can be added and mixedwith the aggregate or the dry cement prior to mixing with water. In awet-phase process, POM fibrous additives can be added to the wetcomponent (cement/water mixture), generally at ambient temperature,prior to combination with the aggregate.

In general, the cementitious composition can contain any suitableaggregate. Aggregates that may be used include, for instance, quartzsand, calcium carbonate, talc, dolomite, aluminum silicates, mica,pumice, perlites, vermiculites, and mixtures thereof. Aggregate cangenerally be present in the cementitious composition in an amount fromabout 10% to about 90% by weight, such as from about 40% to about 90% byweight, such as from about 60% to about 80% by weight.

The concrete can be formed with additional modifiers as are generallyknown in the art. For instance, in addition to the POM fibers,additional fibers such as glass fibers, steel fibers, natural fibers,and polymeric fibers including polyolefins, polyamides (e.g., nylon),and so forth can be incorporated in the concrete. Other modifiersinclude mesh, rebar, cellulose ethers, and the like.

Standard mixing times as are known in the art can be utilized. However,mixing times can vary greatly, as is known, for instance from about fiveminutes to well over an hour, depending on local conditions, specificmaterials, and so forth. Thorough mixing of the materials can randomlydistribute the POM fibrous additives throughout the composition withlittle or no agglomeration of the fibers in the binder.

Following mixing and lying of the cement, the materials can setaccording to standard processes.

Utilization of fibers formed of a composite including POM copolymers canprovide many benefits to a concrete. For instance, POM has higherdensity than polypropylene, which can reduce bloom of the fibers to thesurface during finishing. In addition, POM fibers have higher polarity,resulting in greater miscibility of POM fibers with the concrete matrix.This characteristic can be enhanced when utilizing POM copolymers formedto include a high level of certain terminal groups, e.g., hydroxylgroups. POM fibers can also be drawn to achieve high tenacity values,which can impart improved strength characteristics to a concreteincorporating the fiber. In addition, POM copolymers can be formed toinclude terminal groups that can exhibit bonding to the concrete matrix,which can provide a greater level of reinforcement.

The present disclosure may be better understood by reference to theExamples, below.

Example 1

POM fibers were formed from monomeric reactants as follows:

-   -   1) Polymerization of trioxane with 1,3-dioxolane utilizing a BF₃        initiator and a methylal chain transfer agent—designated POM.    -   2) Polymerization of trioxane with 1,3-dioxolane utilizing a BF₃        initiator and an ethylene glycol chain transfer agent—designated        POM-OH.    -   3) Polymerization of trioxane with glycerol formal formate        utilizing a BF₃ initiator and an ethylene glycol chain transfer        agent—designated lateral OH—POM.

POM fibers were formed utilizing a twin screw reactor with mixing,grinding, and conveying sections. The L/D of the reactor was 15:1. Feedrate was 10000 to 20000 lb/hr. Dioxolane concentration was 3.4 (to 6.2)% (w/w), methylal concentration was about 600 ppm, and BF₃ was 10 to 20ppm. Screw speed was about 30 rpm. The temperature in the reactor wasbetween 90° C. and 95° C. The raw polymer was quenched on exiting thereactor with triethylamine in methanol/water solvent, followed bysolution hydrolysis in a methanol/water (˜80/20) solvent withtriethylamine present to catalyze the hydrolysis. The hydrolyzed polymerwas precipitated from the solution by dropping the pressure (therebycooling the mixture) followed by centrifuging and drying in a series ofdryers. This polymer flake was compounded with standard antioxidant andscavengers. The subsequent pellets were melt spun into fibers, quenchedin air, and drawn to increase tenacity (draw ratio of 5 to 9) and cutinto fiber staple.

POM-OH fibers were formed according to a similar process, except 500-600ppm of ethylene glycol was used in place of methylal. Fiber manufacturewas identical.

Lateral-OH POM was formed in a lab scale unit. Reactor conditions weresimilar to those of the above described processes. Feed rates were inthe range of 2 to 10 kg/hr. The GFF was added at 1 to 2 mol %, alongwith ˜3% dioxolane. Ethylene glycol was used as the chain transferagent.

The three different POM-based microfibers of 4 to 6 denier withtenacities up to 7.5 g/den were formed as described and compared to apolypropylene fiber of the same general size.

Water contact angle for the polypropylene fiber (PP), the POM fiber, andthe POM-OH fiber is compared in FIG. 1. As can be seen, the POM fibersexhibit decreasing values for water contact angle, indicating improvedhydrophilic characteristics.

Example 2

POM, POM-OH, and PP fibers formed as described in Example 1 were mixedwith wet concrete and utilized in an experimental sidewalk pour. Onlythe sections using polypropylene fibers showed a significant fiberconcentration on the surface. This result serves to verify theprediction that the combination of increased hydrophilicity and thehigher density of POM fibers in general will lead to a greatermiscibility of POM fibers over polypropylene fibers in a wet concretematrix.

Example 3

During the sidewalk pour of Example 2, concrete cylinders were also castusing the different concretes that incorporated the different fibers asadditives. Compressive strength measurements of the concrete cylinderswere made. Results are shown in FIG. 2. As can be seen, the observedtrends are consistent with the improved secondary reinforcement to theconcrete provided by the POM fibers, which exhibit increased tenacityand adhesion as compared to the polypropylene fibers.

FIG. 2 shows little difference between polypropylene and POM fibers,indicating that the increase in polarity for POM fibers, while itimproves miscibility, does little to enhance the strength of theconcrete. This is likely due to the low level of —C₂OH end groups instandard POM. On the other hand, the compressive strength of the POM-OHcontaining samples is significantly higher than observed for eitherstandard POM or polypropylene containing samples. This is consistentwith bonding between the —C₂OH end groups on the surface and theconcrete matrix (e.g., —Si—OH moieties).

These and other modifications and variations to the present disclosuremay be practiced by those of ordinary skill in the art, withoutdeparting from the spirit and scope of the present disclosure, which ismore particularly set forth in the appended claims. In addition, itshould be understood that aspects of the various embodiments may beinterchanged either in whole or in part. Furthermore, those of ordinaryskill in the art will appreciate that the foregoing description is byway of example only, and is not intended to limit the disclosure sofurther described in such appended claims.

What is claimed is:
 1. A concrete comprising: an aggregate; acementitious binder; and a plurality of discrete fibers randomlydistributed throughout the concrete, the fibers comprising apolyoxymethylene copolymer in an amount of at least about 50% by weightof the fibers, at least about 50% of the terminal groups of thepolyoxymethylene copolymer being hydroxyl groups, the fibers exhibitinga water contact angle of less than about 30°, the fibers comprisingmicrofibers and/or macrofibers.
 2. The concrete of claim 1, wherein thefibers exhibit a water contact angle of less than about 20°.
 3. Theconcrete of claim 1, wherein the polyoxymethylene copolymer is theproduct of a copolymerization reaction of trioxane with a cyclic acetalcontaining at least one O(CH₂)_(n) group where n is greater than
 1. 4.The concrete of claim 1, wherein the polyoxymethylene copolymer is theproduct of a copolymerization reaction of trioxane with a cyclic formalhaving pendant acrylate or substituted acrylate ester groups.
 5. Theconcrete of claim 1, wherein the polyoxymethylene copolymer is theproduct of a copolymerization reaction of trioxane with a cyclic ester.6. The concrete of claim 1, wherein the polyoxymethylene copolymer isthe product of a copolymerization reaction of trioxane with glycerolformal acetate.
 7. The concrete of claim 1, wherein the polyoxymethylenecopolymer is the product of a copolymerization reaction of trioxane withglycerol formal formate.
 8. The concrete of claim 1, wherein thepolyoxymethylene copolymer comprises three or more different monomerunits.
 9. The concrete of claim 1, wherein the melt index of thepolyoxymethylene copolymer is between about 2 dg/min and about 30dg/min.
 10. The concrete of claim 1, the fibers further comprising animpact modifier.
 11. The concrete of claim 1, the composite comprisingthe microfibers in an amount of from about 1 pound per cubic yard up toabout 3 pounds per cubic yard.
 12. The concrete of claim 1, thecomposite comprising the macrofibers in an amount of from about 2 poundsper cubic yard up to about 8 pounds per cubic yard.
 13. The concrete ofclaim 1, wherein the fibers are deformed fibers.
 14. The concrete ofclaim 1, the composite comprising a mixture of different fibers.
 15. Theconcrete of claim 1, wherein the fibers are less than about 5 inches inlength.
 16. The concrete of claim 1, wherein the fibers are drawnfibers.
 17. A method of forming concrete comprising randomly dispersinga plurality of discrete fibers throughout the concrete, the fiberscomprising a polyoxymethylene copolymer in an amount of at least about50% by weight of the fibers, at least about 50% of the terminal groupsof the polyoxymethylene copolymer being hydroxyl groups, the fibersexhibiting a water contact angle of less than about 30°, the fiberscomprising microfibers and/or macrofibers.
 18. The method according toclaim 17, further comprising forming the fibers from a compositionincluding the polyoxymethylene copolymer.
 19. The method according toclaim 18, wherein the fibers are extruded or spun from a melt of thecomposition.
 20. The method according to claim 18, further comprisingdrawing the fibers.
 21. The method according to claim 17, furthercomprising mixing the fibers with dry cement.
 22. The method accordingto claim 17, further comprising mixing the fibers with wet cement. 23.The concrete of claim 10, wherein the impact modifier comprises athermoplastic elastomer.
 24. The concrete of claim 10, the fibersfurther comprising a coupling agent capable of coupling the impactmodifier to the polyoxymethylene copolymer.
 25. The concrete of claim 1,wherein the macrofibers have a denier of between about 500 denier andabout 4000 denier.
 26. The concrete of claim 1, wherein the microfibershave a denier of between about 1 denier and about 10 denier.
 27. Themethod according to claim 17, wherein the macrofibers have a denier ofbetween about 500 denier and about 4000 denier.
 28. The method accordingto claim 21, wherein the microfibers have a denier of between about 1denier and about 10 denier.